%0 Journal Article %A Van Wyk, Andrea %A Smith, Tanner %A Park, Jaehong %A Deria, Pravas %D 2018 %T Charge-Transfer within Zr-Based Metal–Organic Framework: The Role of Polar Node %U https://acs.figshare.com/articles/journal_contribution/Charge-Transfer_within_Zr-Based_Metal_Organic_Framework_The_Role_of_Polar_Node/5904613 %R 10.1021/jacs.7b13211.s001 %2 https://acs.figshare.com/ndownloader/files/10531999 %K photoelectrochemical devices %K CT reaction %K counterion %K photoexcited MOF linker %K electrochemical experiments %K NU %K material %K CT event %K framework %K MOF-based electrocatalysis %K CT kinetics %K photo-chemical applications %K reorganization energy %K involvement %X Metal–organic frameworks (MOFs) are emerging materials for electro- and photo-chemical applications, where an understanding of the underlying charge-transfer (CT) process will facilitate designing new materials. However, the involvement of counterions in traditional electrochemical experiments complicates the probe on the role of various components during a CT event. A CT reaction between photoexcited MOF linker and a node–anchored ferrocene, within mesoporous framework NU-1000, was spectroscopically probed without the involvement of electrolyte based counterions. Dielectric dependent CT kinetics indicate that the process involves a high reorganization energy that is required to polarize the node bound hydroxyl/aqua ligands. The findings have clear implication on the design of MOF-based electrocatalysis and photoelectrochemical devices. %I ACS Publications